Lithium silicate glass ceramics and lithium silicate glass containing cesium oxide

ABSTRACT

The invention relates to the use of lithium silicate glass ceramics and glasses with caesium oxide content, which are suitable in particular for veneering oxide ceramic restorations and metal restorations.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a National Stage application of International patent application PCT/EP2014/057045 filed on Apr. 8, 2014, which claims priority to European patent application No. 13163830.6 filed on Apr. 15, 2013, the disclosures of which are incorporated herein by reference in their entirety.

The invention relates to lithium silicate glass ceramic and lithium silicate glass which contain caesium oxide and are characterized by a linear coefficient of thermal expansion that is adjustable in a broad range of in particular 8.0 to 17.0·10⁻⁶ K⁻¹ and are therefore suitable primarily in the dental field for veneering oxide ceramic restorations and metal restorations.

In dentistry, dental restorations are usually veneered with ceramic layers in order to match the appearance of the restoration to that of the natural teeth. Such veneered restorations are also called veneer ceramics. In order to avoid stresses between the restoration material to be veneered and the ceramic layer, it is necessary for the coefficients of thermal expansion of the ceramic materials to be adapted to that of the restoration material.

Glass ceramics have already been used in the past to coat or veneer oxide ceramics, such as zirconium oxide ceramics. These include feldspar-based ceramics or fluoroapatite glass ceramics.

Lithium disilicate glass ceramics are also known which, because of their high translucence and very good mechanical properties, are used in particular in the dental field and primarily for producing dental crowns and small bridges. The known lithium silicate glass ceramics usually contain as main components SiO₂, Li₂O, Al₂O₃, Na₂O or K₂O, and nucleating agents such as P₂O₅.

EP 0 885 855 A2 and EP 0 885 856 A2 describe apatite-containing glass ceramics with excellent optical and chemical properties and a strength in the region of 110 MPa, which are suitable for veneering ZrO₂ frameworks.

WO 2004/021921 A1 describes a glass for veneering ZrO₂, but which only has a low strength.

EP 1 253 116 A1 describes a mixture of a lithium silicate glass with leucite crystals for veneering metal frameworks. This glass also has only an inadequate strength.

WO 2012/082156 A1 describes a lithium silicate product for veneering metal frameworks with a coefficient of expansion CTE_(100-400° C.) of from 12 to 13.5·10⁻⁶ K⁻¹ and strengths of up to 300 MPa.

EP 2 377 831 A1 describes a lithium silicate glass ceramic with ZrO₂ content. The coefficient of expansion of the glass ceramic is not suitable for veneering metal frameworks.

In order for a dental glass ceramic to be able to be used for veneering the whole spectrum of the customarily used restoration materials, such as from dental metals and alloys to oxide ceramics, it is necessary for its coefficient of expansion to be adjustable in a broad range. Moreover, the glass ceramics must satisfy high requirements with regard to their optical and mechanical properties and in particular must have a very high strength.

Known glass ceramics and glasses often do not satisfy the requirement for coefficients of thermal expansion that are adjustable in a broad range and for adequate strength. Further, with the known glass ceramics the alkaline earth metal oxide BaO as well as the alkali metal oxides K₂O and/or Na₂O are as a rule present as essential components which are clearly required there for the production of the glass ceramics and in particular the formation of the usually sought lithium disilicate main crystal phase.

There is therefore a need for lithium silicate glass ceramics in which the linear coefficient of thermal expansion CTE_(100-400° C.) is adjustable over a broad range and in particular in the range of from 8.0 to 17.0·10⁻⁶ K⁻¹ and preferably in the range of from 8.8 to 16.7·10⁻⁶ K⁻¹. Further, they should also be able to be produced without the alkali metal oxides K₂O or Na₂O, previously regarded as necessary, as well as in particular without the alkaline earth metal oxide BaO, and be suitable in particular for veneering dental restorations, including oxide ceramic restorations and metal restorations, primarily on the basis of their optical and mechanical properties.

This object is achieved by the use of a lithium silicate glass ceramic or a lithium silicate glass according to any one of claims 1 to 16. A subject of the invention is likewise the method according to claims 17 to 23, the composite material according to claim 24, the lithium silicate glass ceramic according to claims 25 and 26 and the lithium silicate glass according to claim 27. The use according to the invention is characterized in that a lithium silicate glass ceramic or a lithium silicate glass which comprises the following components

component wt.-% SiO₂ 54.0 to 78.0 Li₂O 11.0 to 19.0 Cs₂O 4.0 to 13.0 Al₂O₃ 1.0 to 9.0 P₂O₅ 0.5 to 9.0 is used for coating a substrate selected from oxide ceramics, metals and alloys.

It has surprisingly been shown that the lithium silicate glass ceramic according to the invention has a linear coefficient of thermal expansion CTE_(100-400° C.) which is easily adjustable in a broad range of in particular 8.0 to 17.0·10⁻⁶ K⁻¹ and preferably 8.8 to 16.7·10⁻⁶ K⁻¹, and moreover has excellent optical and mechanical properties such as high strength and fracture toughness. This glass ceramic is therefore suitable for coating both oxide ceramics as well as metals and alloys. It is particularly surprising that the formation of a glass ceramic with lithium meta- and/or disilicate as main crystal phase is successful even in the absence of various components regarded as necessary for conventional glass ceramics, such as in particular K₂O, Na₂O and BaO. The formation of the glass ceramic according to the invention can also be achieved by the use of the lithium silicate glass according to the invention, which represents a precursor for the lithium silicate glass ceramic and can be converted to same before, during or after the application to the substrate.

It is preferred that the lithium silicate glass ceramic used according to the invention and the lithium silicate glass used according to the invention comprise at least one and preferably all of the following components in the given amounts

Component wt.-% SiO₂ 55.1 to 77.1 Li₂O 11.8 to 17.8 Cs₂O 4.4 to 11.7 Al₂O₃ 1.7 to 8.0 P₂O₅ 1.3 to 7.5 ZrO₂ 0 to 4.5, in particular 0 to 4.0 Transition metal oxide 0 to 7.5, in particular 0 to 7.0, wherein the transition metal oxide is selected from the group consisting of oxides of yttrium, oxides of transition metals with an atomic number from 41 to 79 and mixtures of these oxides.

The lithium silicate glass ceramic and the lithium silicate glass preferably comprise up to 70.0 wt.-%, in particular 60.0 to 70.0 wt.-% and preferably 64.0 to 70.0 wt.-% SiO₂.

It is also preferred that the lithium silicate glass ceramic and the lithium silicate glass comprise 12.0 to 17.5, in particular 13.0 to 17.0 and particularly preferably 14.0 to 16.0 wt.-% Li₂O.

In a preferred embodiment, the molar ratio of SiO₂ to Li₂O is from 2.0 to 3.0, in particular from 2.2 to 2.6, preferably from 2.3 to 2.5 and particularly preferably about 2.4. In another preferred embodiment, the molar ratio of SiO₂ to Li₂O is less than 2.0, in particular from 1.5 to 1.9, preferably from 1.6 to 1.8 and particularly preferably about 1.7.

It is preferred that the lithium silicate glass ceramic and the lithium silicate glass comprise 5.0 to 10.0 wt.-%, in particular 5.1 to 8.0 wt.-%, preferably 5.5 to 7.7 wt.-% and particularly preferably 6.1 to 7.4 wt.-% Cs₂O.

It is also preferred that the lithium silicate glass ceramic and the lithium silicate glass comprise 2.0 to 6.0 wt.-%, in particular 2.5 to 5.0 and preferably 3.0 to 4.5 wt.-% Al₂O₃.

The molar ratio of Cs₂O to Al₂O₃ is preferably at least 0.1, in particular from 0.2 to 2.0, preferably from 0.25 to 1.25 and particularly preferably from 0.5 to 1.0.

The glass and the glass ceramic preferably comprise 1.5 to 6.0, in particular 2.0 to 4.0 and preferably 2.5 to 3.5 wt.-% P₂O₅ as nucleating agent.

The lithium silicate glass ceramic used according to the invention and the lithium silicate glass used according to the invention can moreover also comprise additional components which are selected in particular from further oxides of monovalent elements, oxides of divalent elements, further oxides of trivalent elements, further oxides of tetravalent elements, further oxides of pentavalent elements, oxides of hexavalent elements, melt accelerators, colorants and fluorescent agents. In a preferred embodiment, the lithium silicate glass ceramic and the lithium silicate glass comprise additional components in an amount of from 0 to 20.0 wt.-%, in particular 0.1 to 10.0 wt.-%, preferably 0.5 to 7.5 wt.-% and most preferably 1.0 to 5.0 wt.-%.

The term “further oxides of monovalent elements” refers to oxides of monovalent elements and in particular alkali metal oxides with the exception of Li₂O and Cs₂O. Examples of suitable further oxides of monovalent elements are Na₂O, K₂O, Rb₂O and mixtures thereof and in particular Na₂O, K₂O and mixtures thereof.

In one embodiment, the lithium silicate glass ceramic and the lithium silicate glass comprise 0.1 to 2.0 wt.-%, in particular 0.2 to 1.5 wt.-%, preferably 0.3 to 1.4 wt.-% and particularly preferably 0.5 to 1.0 wt.-% Na₂O. In a further embodiment, the lithium silicate glass ceramic and the lithium silicate glass comprise 0.1 to 2.0 wt.-%, in particular 0.2 to 1.6 wt.-%, preferably 0.4 to 1.5 wt.-% and particularly preferably 0.5 to 1.0 wt.-% K₂O. In a particularly preferred embodiment, the lithium silicate glass ceramic and the lithium silicate glass comprise less than 4.0 wt.-%, in particular less than 3.5 wt.-%, preferably less than 3.0 wt.-%, particularly preferably less than 2.5 wt.-% and most preferably less than 2.0 wt.-% Na₂O and/or K₂O.

The lithium silicate glass ceramic and the lithium silicate glass preferably comprise less than 2.5 wt.-%, in particular less than 1.5 wt.-%, preferably less than 1.0 wt.-%, particularly preferably less than 0.5 wt.-% Rb₂O. They are most preferably substantially free of Rb₂O.

In particular the alkaline earth metal oxides, preferably MgO, CaO, SrO, BaO and mixtures thereof, and preferably CaO, SrO and mixtures thereof, come into consideration as oxides of divalent elements.

The lithium silicate glass ceramic and the lithium silicate glass preferably comprise less than 3.8 wt.-%, in particular less than 2.5 wt.-%, preferably less than 1.5 wt.-%, particularly preferably less than 0.5 wt.-% BaO. They are most preferably substantially free of BaO.

The term “further oxides of trivalent elements” refers to oxides of trivalent elements with the exception of Al₂O₃. Suitable oxides of trivalent elements are in particular Y₂O₃, La₂O₃, Bi₂O₃ and mixtures thereof, and preferably Y₂O₃ and La₂O₃.

The term “further oxides of tetravalent elements” refers to oxides of tetravalent elements with the exception of SiO₂. Examples of suitable further oxides of tetravalent elements are TiO₂, GeO₂ and ZrO₂.

The term “further oxides of pentavalent elements” refers to oxides of pentavalent elements with the exception of P₂O₅. Examples of suitable further oxides of pentavalent elements are Ta₂O₅ and Nb₂O₅.

Examples of suitable oxides of hexavalent elements are WO₃ and MoO₃.

A glass and a glass ceramic which comprises at least one further oxide of monovalent elements, one oxide of divalent elements, at least one further oxide of trivalent elements, at least one further oxide of tetravalent elements, at least one further oxide of pentavalent elements and/or at least one oxide of hexavalent elements are preferred.

Examples of melt accelerators are fluorides.

Examples of colorants and fluorescent agents are oxides of d- and f-elements, such as e.g. the oxides of Ti, V, Sc, Mn, Fe, Co, Ta, W, Ce, Pr, Nd, Tb, Er, Dy, Gd, Eu and Yb. Metal colloids, e.g. of Ag, Au and Pd, can also be used as colorants and in addition can also act as nucleating agents. These metal colloids can be formed e.g. by reduction of corresponding oxides, chlorides or nitrates during the melting and crystallization processes. The metal colloids are preferably present in the glass ceramic in an amount of from 0.005 to 0.5 wt.-%.

The glass ceramic used according to the invention preferably has lithium metasilicate and/or lithium disilicate as main crystal phase. The term “main crystal phase” denotes the crystal phase which has the highest proportion by volume compared with the other crystal phases. If two crystal phases have about the same proportion by volume, these crystal phases can both be present as main crystal phases. In other embodiments, lithium metasilicate can be present as main crystal phase and lithium disilicate as secondary phase or lithium disilicate as main crystal phase and lithium metasilicate as secondary phase.

It has surprisingly been shown that the lithium silicate glass ceramic according to the invention has very good mechanical and optical properties even in the absence of components regarded as necessary for conventional glass ceramics. The combination of their properties even allows them to be used as dental material and in particular for coating dental restorations.

The lithium silicate glass ceramic according to the invention preferably has a fracture toughness, measured as K_(IC) value, of at least about 2.0 MPa·m^(0.5), in particular at least about 2.3 MPa·m^(0.5) and preferably at least about 2.6 MPa·m^(0.5). This value was determined using the Vickers method and calculated using Niihara's equation. Further, it has a high biaxial breaking strength of preferably 180 to 700 MPa. Moreover, it displays a high chemical resistance ascertained by mass loss after storage in acetic acid. The chemical stability is in particular less than 100 μg/cm². The biaxial breaking strength and the chemical staility were determined according to ISO 6872 (2008).

In a preferred embodiment, the glass ceramic comprises lithium metasilicate as main crystal phase. In particular the glass ceramic comprises more than 5 vol.-%, preferably more than 10 vol.-% and particularly preferably more than 15 vol.-% lithium metasilicate crystals, relative to the total glass ceramic. This lithium metasilicate glass ceramic is characterized by very good mechanical properties. It preferably has a bending strength in the range of about 180 to 300 MPa and/or a fracture toughness, measured as K_(IC) value, of at least about 2.0 MPa·m^(0.5), in particular at least about 2.3 MPa·m^(0.5) and preferably at least about 2.6 MPa·m^(0.5). It can be formed e.g. by heat treatment of a corresponding lithium silicate glass and in particular of a corresponding lithium silicate glass with nuclei.

In a further particularly preferred embodiment, the glass ceramic comprises lithium disilicate as main crystal phase. In particular the glass ceramic comprises more than 10 vol.-%, preferably more than 20 vol.-% and particularly preferably more than 30 vol.-% lithium disilicate crystals, relative to the total glass ceramic. This lithium disilicate glass ceramic is characterized by particularly good mechanical properties. It preferably has a bending strength in the range of about 400 to 700 MPa and/or a fracture toughness, measured as K_(IC) value, of at least about 2.0 MPa·m^(0.5), in particular at least about 2.3 MPa·m^(0.5) and preferably at least about 2.6 MPa·m^(0.5). It can be produced e.g. by heat treatment of the lithium metasilicate glass ceramic. However, it can also be formed by heat treatment of a corresponding lithium silicate glass or a corresponding lithium silicate glass with nuclei.

It is preferred according to the invention that the lithium silicate glass ceramic has at least one caesium aluminosilicate crystal phase. It has surprisingly been shown that such a crystal phase improves the adjustability of the coefficient of thermal expansion in particular to higher values. The caesium aluminosilicate preferably has the formula Cs_(x)AlSi₅O₁₂, wherein x is 0.70 to 0.90, in particular 0.75 to 0.85, preferably 0.80 to 0.82 and particularly preferably 0.808 to 0.810. Most preferred is a caesium aluminosilicate which has the formula Cs_(0.809)AlSi₅O₁₂.

In a particularly preferred embodiment, a lithium silicate glass ceramic is used which furthermore comprises a lithium aluminosilicate crystal phase. It has surprisingly been shown that such a crystal phase improves the adjustability of the coefficient of thermal expansion in particular to lower values. The lithium aluminosilicate preferably has the formula Li₂O*Al₂O₃*7.5SiO₂.

In particular Li₃PO₄, SiO₂ and TiO₂ come into question as further crystal phases of the lithium silicate glass ceramic.

In a further embodiment, a lithium silicate glass is used. This lithium silicate glass preferably comprises nuclei which are suitable for the formation of lithium metasilicate and/or lithium disilicate crystals. Such a lithium silicate glass with nuclei can be formed in particular by heat treatment of a corresponding lithium silicate glass. The lithium metasilicate glass ceramic according to the invention can then be formed by a further heat treatment, and in turn be converted to the lithium disilicate glass ceramic according to the invention by further heat treatment, or the lithium disilicate glass ceramic according to the invention can also preferably be formed directly from the glass with nuclei. Consequently, the lithium silicate glass, the lithium silicate glass with nuclei and the lithium metasilicate glass ceramic can be regarded as precursors for producing a high-strength lithium meta- or disilicate glass ceramic according to the invention. The lithium silicate glass is preferably converted to a glass ceramic as described above before, during or after application to the substrate.

To produce the lithium silicate glass, the procedure can be in particular that a mixture of suitable starting materials, such as carbonates, oxides, phosphates and fluorides, is melted at temperatures of in particular 1300 to 1600° C. for 2 to 10 h. To achieve a particularly high homogeneity, the obtained glass melt is poured into water in order to form a glass granulate, and the obtained granulate is then melted again. The melt can then be poured into moulds to produce blanks of the lithium silicate glass, so-called solid glass blanks or monolithic blanks. It is also possible to put the melt into water again in order to produce a granulate. This granulate can then be pressed, after grinding and optionally addition of further components, such as colorants and fluorescent agents, to form a blank, a so-called powder green compact. Finally, the lithium silicate glass can also be processed to form a powder after granulation.

The lithium silicate glass, e.g. in the form of a solid glass blank, a powder green compact or in the form of a powder, is then subjected to at least one heat treatment in the range of from 450 to 1050° C. It is preferred that a first heat treatment is initially carried out at a temperature in the range of from 480 to 580° C., in particular 480 to 560° C. and preferably 480 to 520° C. to produce a glass with nuclei which are suitable for forming lithium metasilicate and/or lithium disilicate crystals. This first heat treatment is preferably carried out for a period of from 5 to 120 minutes, in particular 10 to 60 minutes and preferably 10 to 30 minutes. The glass with nuclei can then preferably be subjected to at least one further temperature treatment at a higher temperature and in particular more than 580° C. to effect crystallization of lithium metasilicate or lithium disilicate. This further heat treatment is preferably carried out for a period of from 10 to 120 minutes, in particular 10 to 60 minutes and particularly preferably 20 to 30 minutes. To crystallize lithium metasilicate, the further heat treatment is usually carried out at 600 to 950° C., preferably 620 to 850° C. and particularly preferably 650 to 750° C. To crystallize lithium disilicate, the further heat treatment is usually carried out at 750 to 1050° C., preferably 800 to 1000° C., particularly preferably 820 to 950° C. and quite particularly preferably 850 to 900° C.

The lithium silicate glass ceramic used according to the invention and the lithium silicate glass used according to the invention are present in particular in the form of powders, granulates or blanks, e.g. monolithic blanks, such as discs, cuboids or cylinders, or powder green compacts, in unsintered, partly sintered or densely-sintered form. They can easily be further processed in these forms. However, they can also be present in the form of an overstructure for dental restorations, such as in particular crowns. It is preferred that the glass ceramic or the glass is shaped into the desired geometry by machining or pressing.

The lithium silicate glass ceramic used according to the invention and the lithium silicate glass used according to the invention are suitable in particular for coating oxide ceramics, metals and alloys.

In a preferred embodiment, the substrate is an oxide ceramic. Zirconium oxide ceramics are particularly preferred. Examples of suitable zirconium oxide ceramics are ceramics based on polycrystalline tetragonal zirconium oxide (tetragonal zirconia polycrystal, TZP) in which the tetragonal form is stabilized by the addition of Y₂O₃ and/or CeO₂.

In another preferred embodiment, the substrate is a metal or an alloy. Non-precious metal alloys and in particular non-ferrous alloys which are suitable for dental applications are particularly preferred. Examples of suitable alloys are in particular alloys of the Ni—Cr, Co—Cr and Co—Cr—W type.

It is furthermore preferred that the substrate is a dental restoration and in particular a bridge, an inlay, an onlay, a veneer, an abutment, a partial crown, a crown or a facet.

The invention also relates to a process for coating a substrate selected from oxide ceramics, metals and alloys, in which a lithium silicate glass ceramic as described above or a lithium silicate glass as described above are applied to the substrate. The substrate is preferably as described above.

In an embodiment of the process according to the invention, the lithium silicate glass ceramic or the lithium silicate glass is applied to the substrate by sintering and preferably by pressing-on.

During sintering, the lithium silicate glass ceramic according to the invention or the lithium silicate glass according to the invention is applied in customary manner, e.g. as powder, to the material to be coated and then sintered at increased temperature.

During the preferred pressing-on, the lithium silicate glass ceramic according to the invention or the lithium silicate glass according to the invention, e.g. in the form of powder green compacts or monolithic blanks, is converted to a viscous state at an increased temperature of e.g. 700 to 1200° C. and pressed onto the substrate using low pressure, e.g. 2 to 10 bar. For this, in particular the methods described in EP 231 773 A1 and the press furnace disclosed there can be used. A suitable furnace is e.g. the Programat EP 5000 from Ivoclar Vivadent AG.

In another embodiment of the process according to the invention, the lithium silicate glass ceramic or the lithium silicate glass is applied to the substrate by joining. Suitable joining methods are known per se and comprise for example joining by means of a glass or glass ceramic solder, joining by adhesion by means of an adhesive or dental cement, joining by sagging by means of a temperature treatment in which the materials to be joined are softened, and joining by friction welding or wringing.

In a particularly preferred embodiment, the lithium silicate glass ceramic or the lithium silicate glass is shaped to a desired geometry by hot pressing or by machining before joining.

The hot pressing is usually carried out under increased pressure and increased temperature. It is preferred that the hot pressing is carried out at a temperature of from 700 to 1200° C. It is further preferred to carry out the hot pressing at a pressure of from 2 to 10 bar. The desired shape change is achieved by viscous flow of the material used. The lithium metasilicate glass ceramic according to the invention, the lithium disilicate glass ceramic according to the invention, the lithium silicate glass according to the invention and in particular the lithium silicate glass with nuclei according to the invention can be used for the hot pressing. The glass ceramics and glasses can be used in particular in the form of blanks, e.g. solid blanks or powder green compacts, e.g. in unsintered, partly sintered or densely-sintered form.

The machining is usually carried out by material removal processes and in particular by milling and/or grinding. It is particularly preferred that the machining is carried out as part of a CAD/CAM process. For the machining, the lithium silicate glass, the lithium silicate glass with nuclei, the lithium metasilicate and lithium disilicate glass ceramic can be used. The glasses and glass ceramics can be used in particular in the form of blanks, e.g. solid blanks or powder green compacts, e.g. in unsintered, partly sintered or densely-sintered form. For the machining, lithium silicate glass ceramic in particular with lithium disilicate and preferably with lithium metasilicate as main crystal phase is preferably used. The lithium silicate glass ceramic can also be used in a not yet fully crystallized form which was produced by heat treatment at a lower temperature. This has the advantage that an easier machining and thus the use of simpler equipment for the machining is possible. After the machining of such a partly crystallized material, the latter is usually subjected to a heat treatment at a higher temperature and in particular 750 to 1050° C., preferably 800 to 950° C. and particularly preferably about 850 to 900° C. in order to effect further crystallization of lithium metasilicate or preferably lithium disilicate.

In general, the lithium silicate glass ceramic or the lithium silicate glass can also in particular be heat-treated after the shaping by hot pressing or machining, in order to convert precursors used, such as lithium silicate glass, lithium silicate glass with nuclei or lithium metasilicate glass ceramic, to lithium meta- and/or disilicate glass ceramic, increase the crystallization of lithium meta- and/or disilicate, or reduce the porosity e.g. of a porous powder green compact used.

It is preferred that, after the coating procedure has been completed, a coating is obtained which comprises a lithium silicate glass ceramic with lithium meta- and/or disilicate as main crystal phase as it has particularly good properties. Glass ceramics which have the crystal phases and mechanical properties described above are particularly preferred.

Furthermore, the invention relates to a composite material which comprises a lithium silicate glass ceramic as defined above or a lithium silicate glass as defined above on a substrate selected from oxide ceramics, metals and alloys. All embodiments are preferred which are also mentioned as preferred for the lithium silicate glass ceramic used according to the invention, the lithium silicate glass used according to the invention as well as the substrate. The composite material can be produced in particular by means of the process according to the invention.

The invention also relates to a lithium silicate glass ceramic which comprises the following components

Component wt.-% SiO₂ 54.0 to 78.0, in particular 55.1 to 77.1 Li₂O 11.0 to 19.0, in particular 11.8 to 17.8 Cs₂O 4.6 to 13.0, in particular 4.7 to 11.7 Al₂O₃ 1.0 to 9.0, in particular 1.7 to 8.0 P₂O₅ 0.5 to 9.0, in particular 1.3 to 7.5 Rb₂O 0 to 7.0, in particular 0 to 5.0 BaO 0 to 3.7, in particular 0 to 3.0 ZrO₂ 0 to 4.5, in particular 0 to 4.0 Transition metal oxide 0 to 7.5, in particular 0 to 7.0,

wherein the transition metal oxide is selected from the group consisting of oxides of yttrium, oxides of transition metals with an atomic number from 41 to 79 and mixtures of these oxides.

Moreover, the invention also relates to a lithium silicate glass which comprises the components of the above glass ceramic.

In addition, the lithium silicate glass and the lithium silicate glass ceramic can also comprise still further components such as are given above for the lithium silicate glass ceramic used according to the invention and the lithium silicate glass used according to the invention. All embodiments are preferred which are also mentioned as preferred for the lithium silicate glass ceramic used according to the invention and the lithium silicate glass used according to the invention.

The invention is explained in more detail below by means of examples.

EXAMPLES

A total of 28 glasses and glass ceramics according to the invention with the compositions given in Table I were produced by melting corresponding starting glasses followed by heat treatment for controlled nucleation and crystallization.

For this, the starting glasses in amounts of 100 to 200 g were first melted from customary raw materials at 1450 to 1550° C., wherein the melting was very easily possible without formation of bubbles or streaks. By pouring the starting glasses into water, glass frits were produced which were then melted a second time at 1450 to 1550° C. for 1 to 3 h for homogenization. The obtained glass melts were then poured into pre-heated moulds to produce glass monoliths. All glass monoliths proved transparent.

The glass monoliths were then converted to glasses and glass ceramics according to the invention by thermal treatment. The thermal treatments used for controlled nucleation and controlled crystallization are also given in Table I. The following meanings apply

T_(N) and t_(N) Temperature and time used for nucleation T_(C) and t_(C) Temperature and time used for first crystallization T_(FC) and t_(FC) Temperature and time used for final crystallization T_(press) and t_(press) Temperature and time used for hot pressing

It can be seen that a first heat treatment in the range of from 470 to 580° C. resulted in the formation of lithium silicate glasses with nuclei and these glasses crystallized as a result of a further heat treatment at 600 to 750° C. to form glass ceramics with lithium metasilicate as main crystal phase, as was established by X-ray diffraction tests. Only in the case of Examples 8, 11 and 12 was lithium disilicate (also) formed as main crystal phase. A final heat treatment at a temperature of from 840 to 950° C. finally resulted predominantly in the formation of glass ceramics with lithium disilicate as main crystal phase. In the case of Examples 3, 5 and 9, glass ceramics with lithium metasilicate as main crystal phase were obtained.

The produced lithium disilicate glass ceramics had high fracture toughness values, measured as critical stress intensity factor K_(IC) according to the SEVNB method, of more than 2.0 MPa·m^(0.5) and in particular even at least 2.6 MPa·m^(0.5).

The biaxial strength GB was also high, at at least 250 MPa and up to more than 600 MPa. It was determined according to dental standard ISO 6872 (2008) on test pieces that were produced by machining of the respective lithium disilicate glass ceramic. A CEREC-InLab machine (Sirona, Bensheim) was used for the processing.

They were also able to be applied by hot pressing as coatings onto in particular oxide ceramic restorations or metal restorations, e.g. in order to veneer them as desired.

Some examples are described in more detail below:

Example 10

From a mixture of the raw materials with the composition given in Table I for Example 10, a glass was melted at a temperature of 1500° C. for 2 h and a glass frit was produced by subsequent pouring into water. After drying the glass frit in the drying furnace up to 750° C., it was melted again at 1500° C. for 2.5 h and then poured into graphite moulds in order to produce glass monoliths. Immediately after demoulding the hot glass monoliths, they were stress-relieved and nucleated for 10 min at 500° C. and then slowly cooled to room temperature.

Before further processing, the glass blocks were converted to a lithium metasilicate glass ceramic. For this, the glass blocks were placed in a furnace preheated to 400° C. After a residence time of 20 min, the temperature was increased to 700° C. at a heating rate of 10 K/min and this temperature was maintained for 20 min. The blocks were then slowly cooled to room temperature in the closed furnace.

In order to facilitate a CAM processing of the metasilicate blocks by means of Sirona inLab grinding machines, the corresponding holders were glued to the blocks. The grinding processing was carried out with diamond-coated grinding tools. Small discs with a diameter of about 12 mm and a thickness of about 2 mm were ground from the blocks.

The conversion of the ground bodies from the metasilicate state to the disilicate state was carried out via a further thermal treatment. The bodies were heated in a Programat-type furnace (Ivoclar Vivadent AG) to a temperature of 920° C. and, after a residence time of 7 min, cooled slowly to a temperature of 400° C. and removed from the furnace. The XRD analysis of the thus-produced material displayed, in addition to the main phase Li₂Si₂O₅, the secondary phase Cs_(0.809) (AlSi₅O₁₂), among others, which is responsible for a high coefficient of thermal expansion of the glass ceramics. The thus-produced glass ceramic is thereby suitable for joining to metals and metal alloys. The crystallized discs were then ground with diamond grinding wheels to a thickness of about 1.2 mm and polished to 0.5 μm. The biaxial strength was then determined on the thus-produced and prepared samples. An average strength of 608 MPa was measured.

Example 14

From a mixture of the raw materials with the composition given in Table I for Example 14, a glass was melted at a temperature of 1500° C. for 2 h and a glass frit was produced by subsequent pouring into water. The dried glass frit was then melted again at 1500° C. for 2.5 h and then poured into graphite moulds to produce glass monoliths. The stress relief and nucleation of the thus-produced glass blocks was carried out immediately after the demoulding at 500° C. for 10 min, followed by a slow cooling to room temperature.

Before further processing, the glass blocks were converted to the metasilicate state. For this, the glass blocks were placed in a furnace preheated to 400° C. After a residence time of 20 min, the temperature was increased to 600° C. at a heating rate of 10 K/min and this temperature was maintained for 120 min. The blocks were then slowly cooled to room temperature in the closed furnace. An X-ray structural analysis was carried out on the thus-crystallized blocks. Li₂SiO₃ was identified as main crystal phase.

In order to facilitate a CAM processing of the metasilicate blocks by means of Sirona inLab grinding machines, the corresponding holders were glued to the blocks. The grinding processing was carried out with diamond-coated grinding tools. Small discs with a diameter of about 12 mm and a thickness of about 2 mm were ground from the blocks.

The conversion of the ground bodies from the metasilicate state to the disilicate state was carried out via a further thermal treatment. The bodies were heated in a Programat-type furnace (Ivoclar Vivadent AG) to a temperature of 905° C. and, after a residence time of 30 min, cooled slowly to a temperature of 400° C. and removed from the furnace. An XRD analysis of the thus-treated material displayed, in addition to the main crystal phase Li₂Si₂O₅, a lithium aluminosilicate secondary phase, among others. The linear coefficient of thermal expansion CTE_(100-400° C.) was 9.0-10⁻⁶ K⁻¹. Because of the low coefficient of thermal expansion, the thus-produced glass ceramic is suitable for joining to zirconium oxide ceramics.

Example 15

From a mixture of the raw materials with the composition given in Table I for Example 15, a glass was melted at a temperature of 1500° C. for 2 h and a glass frit was produced by subsequent pouring into water. The dried glass frit was then melted again at 1500° C. for 2.5 h and then poured into graphite moulds to produce glass monoliths. The stress relief and nucleation of the thus-produced glass blocks were carried out immediately after the demoulding at 500° C. for 10 min, followed by a slow cooling to room temperature.

a) CAM Processing of Metasilicate Blocks and Conversion to Lithium Disilicate

For the conversion to the metasilicate state, the glass blocks were placed in a furnace preheated to 400° C. After a residence time of 20 min, the temperature was increased to 650° C. at a heating rate of 10 K/min and this temperature was maintained for 60 min. The blocks were then slowly cooled to room temperature in the closed furnace. An X-ray structural analysis was carried out on the thus-crystallized blocks. Li₂SiO₃ was identified as main crystal phase.

In order to facilitate a CAM processing of the metasilicate blocks by means of Sirona inLab grinding machines, the corresponding holders were glued to the blocks. The grinding processing was carried out with diamond-coated grinding tools. Small discs with a diameter of about 12 mm and a thickness of about 2 mm were ground from the blocks.

The conversion of the ground bodies from the metasilicate state to the disilicate state was carried out via a further thermal treatment. The bodies were heated in a Programat-type furnace (Ivoclar Vivadent AG) to a temperature of 920° C. and, after a residence time of 60 min, cooled slowly to a temperature of 400° C. and removed from the furnace. The XRD analysis of the thus-produced material displayed, in addition to the main phase Li₂Si₂O₅, the secondary phase Cs_(0.809) (AlSi₅O₁₂), among others. The linear coefficient of thermal expansion CTE_(100-400° C.) was 13.1·10⁻⁶ K⁻¹. The thus-produced glass ceramic is therefore suitable for joining to metals and metal alloys.

The crystallized discs were then ground with diamond grinding wheels to a thickness of about 1.2 mm and polished to 0.5 μm. A biaxial strength was then determined on the thus-produced and prepared samples. An average strength of 350 MPa was measured.

b) CAM Processing of Metasilicate Blocks, Conversion to Lithium Disilicate and Joining to Alloy

A further glass block was converted via a temperature treatment at 600° C. for 120 min to a glass ceramic with the main crystal phase Li₂SiO₃. The metasilicate block was then provided with a holder suitable for processing by Sirona inLab grinding machines and an overstructure was ground from the block. The overstructure was then converted to the disilicate state by a temperature treatment at 940° C. for 15 min. A framework structure of the alloy d.SIGN® 30 (Ivoclar Vivadent AG) was covered with the opaquer IPS Classic (Ivoclar Vivadent AG) and then fired. With the help of a silicate glass ceramic solder with a coefficient of thermal expansion of about 13.5·10⁻⁶ K⁻¹, the framework was then joined to the overstructure at a joining temperature of 800° C. for 7 min.

Example 22

From a mixture of the raw materials with the composition given in Table I for Example 22, a glass was melted at a temperature of 1500° C. for 2 h and a glass frit was produced by subsequent pouring into water. After drying the glass frit in the drying furnace, it was melted again at 1500° C. for 2 h and then poured into graphite moulds in order to produce glass monoliths. Immediately after demoulding the hot glass monoliths, they were stress-relieved and nucleated for 10 min at 480° C. and then slowly cooled to room temperature.

a) CAM Processing of Metasilicate Blocks and Conversion to Lithium Disilicate

In order to facilitate a CAM processing of the metasilicate blocks by means of Sirona inLab grinding machines, the corresponding holders were glued to the blocks. The grinding processing was carried out with diamond-coated grinding tools. Small discs with a diameter of about 12 mm and a thickness of about 2 mm were ground from the blocks.

The conversion of the ground bodies to the disilicate state was carried out via a thermal treatment. The bodies were heated in a Programat-type furnace (Ivoclar Vivadent AG) to a temperature of 900° C. and, after a residence time of 7 min, cooled slowly to a temperature of 400° C. and removed from the furnace.

The crystallized discs were then ground with diamond grinding wheels to a thickness of about 1.2 mm and polished to 0.5 μm. The biaxial strength was then determined on the thus-produced and prepared samples. An average strength of 319 MPa was measured.

b) Hot Pressing of Nucleated Glass to Form Restorations

For the hot pressing, plastic (PMMA) restorations of various geometries were embedded in a dental embedding compound, the plastic was burned out and the nucleated glass blocks were pressed within 2.29 min at a temperature of 950° C. (residence time 25 min) and using an EP5000. After the cooling had completed, the restorations were devested with a sandblaster and separated from their compression channels and ground. The linear coefficient of thermal expansion CTE_(100-400° C.) was 11.9·10⁻⁶ K⁻¹.

Example 23A

A mixture of oxides and carbonates with the composition given in Table I for Example 23 was first mixed in a Speed Mixer for 2 minutes and then melted at 1500° C. for 2 h in a platinum/rhodium crucible (Pt/Rh-90/10). The melt was then poured into water in order to obtain a fine-particle granulate which was melted again for 2 h at 1500° C. after drying in order to improve the homogeneity. Cylindrical glass blanks with a diameter of 12.5 mm were then poured into pre-heated, separable steel moulds, transferred to a furnace preheated to 470° C. and stress-relieved for 10 min. In this way, a glass with nuclei was obtained.

a) Hot Pressing of Nucleated Glass to Form Restorations

For the hot pressing, plastic (PMMA) restorations of various geometries were embedded in a dental embedding compound, the plastic was burned out and the nucleated glass cylinders were pressed within 4.20 min at a temperature of 920° C. (residence time 25 min) and using an EP5000. After the cooling had completed, the restorations were devested with a sandblaster and separated from their compression channels and ground. The linear coefficient of thermal expansion CTE_(100-400° C.) was 12.1·10⁻⁶ K⁻¹.

b) Hot Pressing of Nucleated Glass on Alloy

The glass with nuclei was crystallized for 30 min at 890° C. and pressed onto a metal alloy d.Sign 30 (Ivoclar Vivadent AG) by hot pressing at 940° C. in a Programat EP 5000-type furnace (Ivoclar Vivadent AG). A ZrO₂-containing opaquer from the IPS Classic® line (Ivoclar Vivadent AG) was used as intermediate layer between metal and pressed glass ceramic. After the pressing process, a defect-free surface was achieved. Thus, this glass ceramic is suitable for pressing over dental crowns of non-precious metal alloys, in particular Co—Cr and Ni—Cr alloys.

Example 23B

From the raw materials of Example 23, a glass was melted at temperatures between 1450 and 1550° C. for 1 to 3 h and a glass frit was produced by subsequent pouring into water. After drying the glass frit in the drying furnace, it was comminuted to a particle size of <45 μm.

a) Coating Glass Powder onto Alloy and Sintering

The glass powder was mixed with a modelling fluid and the mixture was applied to a single tooth crown of the alloy IPS d.SIGN® 30 (Ivoclar Vivadent AG). The opaquer from the IPS Classic® line (Ivoclar Vivadent AG) was used as intermediate layer between metal and coated powder. The coated-on mixture was then sintered twice in a P100 dental furnace (Ivoclar Vivadent AG) at a holding temperature of 850° C. and a residence time of 5 min (2 corrective firings). The sintering was followed by the application of universal glaze (Ivoclar Vivadent AG) and a glaze firing at 850° C. and a residence time of 5 min.

b) Coating of a Sintered Glass onto Alloy and Sintering

The glass powder was processed to form blanks with a weight of 40 g and sintered for one hour at 940° C. The sintered body was then cooled in air for 1.30 min and then quenched in water and dried. This sintered body was comminuted again to a particle size of <45 μm and, analogously to the glass powder, coated onto a single tooth crown of the metal alloy IPS d.SIGN® 30. The opaquer from the IPS Classic® line (Ivoclar Vivadent AG) was likewise used as intermediate layer between metal and coated powder. The corrective firings were carried out at 900° C. for 5 min.

Example 26

A mixture of oxides and carbonates with the composition given in Table I for Example 26 was first mixed in a Speed Mixer for 2 minutes and then melted at 1500° C. for 2 h in a platinum/rhodium crucible (Pt/Rh-90/10). The melt was then poured into water in order to obtain a fine-particle granulate which, after drying, was melted again for 2 h at 1500° C. in order to improve the homogeneity. Cylindrical glass blanks with a diameter of 12.5 mm were then poured into pre-heated, separable steel moulds and transferred to a furnace preheated to 480° C. and stress-relieved for 10 minutes. In this way, a glass with nuclei was obtained.

a) Hot Pressing of Nucleated Glass to Form Restorations

For the hot pressing, plastic (PMMA) restorations of various geometries were embedded in a dental embedding compound, the plastic was burned out and the nucleated glass cylinders were pressed within 1.25 min at a temperature of 930° C. (residence time 25 min) and using an EP5000. After the cooling had completed, the restorations were devested with a sandblaster and separated from their compression channels and ground. The linear coefficient of thermal expansion CTE_(100-400° C.) was 12.1·10⁻⁶ K⁻¹.

b) Hot Pressing onto Zirconium Oxide Ceramic

The glass was applied by hot pressing at 940° C. to a zirconium oxide ceramic of the type 3Y-TZP (Tosoh, Japan) in a Programat EP5000 press furnace (Ivoclar Vivadent AG). After completion of the coating process, a defect-free glass ceramic crown was obtained.

TABLE I Example 1 2 3 4 5 6 7 8 9 10 Composition wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% SiO₂ 68.3 69.8 59.8 70.4 57.5 69.1 70.4 71.9 55.1 74.1 Li₂O 14.2 14.5 17.0 14.6 17.1 14.4 14.6 14.9 16.0 15.5 Cs₂O 11.1 9.2 10.8 8.0 11.7 9.8 8.1 5.7 10.0 5.1 Al₂O₃ 3.3 3.3 4.0 3.2 4.0 3.6 3.2 3.3 4.0 1.9 P₂O₅ 3.1 3.2 3.4 3.4 3.4 3.1 3.4 3.4 3.3 3.4 Na₂O — — 0.9 — — — 0.3 0.8 — — K₂O — — — 0.4 — — — — — — CaO — — — — — — — — — — SrO — — — — — — — — — — ZnO — — — — — — — — — — Y₂O₃ — — 3.0 — — — — — — — La₂O₃ — — — — — — — — — TiO₂ — — — — — — — — — — GeO₂ — — — — — — — — 8.0 — ZrO₂ — — — — 4.5 — — — 1.0 — CeO₂ — — 1 — 1.0 — — — 0.9 — V₂O₅ — — 0.1 — 0.1 — — — 0.1 — Ta₂O₅ — — — — — — — — 1.0 — Tb₄O₇ — — — — 0.5 — — — 0.3 — Er₂O₃ — — — — 0.2 — — — 0.3 — B₂O₃ — — — — — — — — — — F — — — — — — — — — — T_(g)/° C. 492 474 462 492 476 482 472 465 464 477 T_(N)/° C. 510 510 480 510 500 500 490 480 480 500 t_(N)/min 10 10 10 10 10 10 10 10 10 10 T_(c)/° C. 700 700 680 700 720 700 700 700 660 700 t_(c)/min 20 20 40 20 20 20 10 20 60 20 Main Li₂SiO₃ Li₂SiO₃ Li₂SiO₃ Li₂SiO₃ Li₂SiO₃ Li₂SiO₃ Li₂SiO₃ Li₂SiO₃ Li₂SiO₃ Li₂SiO₃ crystal Li₂Si₂O₅ phase Other Li₂Si₂O₅ crystal phases T_(FC)/° C. 920 900 930 900 910 910 880 840 910 920 t_(FC)/min 7 7 10 7 30 7 7 7 10 7 T_(press)/° C. t_(Press)/min Main Li₂Si₂O₅ Li₂Si₂O₅ Li₂SiO₃ Li₂Si₂O₅ Li₂SiO₃ Li₂Si₂O₅ Li₂Si₂O₅ Li₂Si₂O₅ Li₂SiO₃ Li₂Si₂O₅ crystal phase Other Li₂SiO₃ Li₂SiO₃ Li₃PO₄ Li₃PO₄ Li₃PO₄ Li₂SiO₃ Li₃PO₄ Li₃PO₄ Li₃PO₄ Li₃PO₄ crystal Li₃PO₄ Li₃PO₄ CAS CAS CAS Li₃PO₄ CAS CAS CAS CAS phases CAS CAS CAS L* a* b* CR CTE_(100-400° C.)/ 13.3 12.9 12.4 11.7 13.6 12.4 11.3 12.2 16.1 10⁻⁶ · K⁻¹ K_(IC)/ 2.8 MPa m^(0.5) σ_(B)/MPa 385 470 338 253 432 352 608 CAS = Cs_(0.809) (AlSi₅O₁₂) L*,a*,b*: colour coordinates of the samples, determined according to DIN 5033 and DIN 6174 CR: contrast value as a measure of the translucence, determined according to BS 5612 Example 11 12 13 14 15 16 17 18 19 20 Composition wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% SiO₂ 74.1 71.7 77.1 71.5 67.1 66.8 64.9 65.9 75.8 71.0 Li₂O 15.5 17.8 12.8 14.9 13.9 13.9 13.5 13.7 15.8 14.8 Cs₂O 5.1 5.2 5.0 5.0 10.9 4.6 10.6 9.4 5.2 4.9 Al₂O₃ 1.9 1.9 1.8 5.4 3.2 1.7 3.1 8.0 1.9 1.8 P₂O₅ 3.4 3.4 3.3 3.2 3.0 3.0 3.0 3.0 1.3 7.5 Na₂O — — — — — — — — — — K₂O — — — — — — — — — — CaO — — — — — — — — — — SrO — — — — — 3.0 — — — — ZnO — — — — — — — — — — Y₂O₃ — — — — — — 3.0 — — — La₂O₃ — — — — — 3.0 — — — — TiO₂ — — — — — 4.0 — — — — GeO₂ — — — — — — — — — — ZrO₂ — — — — — — — — — — CeO₂ — — — — 1.8 — 1.8 — — — V₂O₅ — — — — 0.1 — 0.1 — — — Ta₂O₅ — — — — — — — — — — Tb₄O₇ — — — — — — — — — — Er₂O₃ — — — — — — — — — — B₂O₃ — — — — — — — — — — F — — — — — — — — — — T_(g)/° C. 477 464 483 475 476 490 492 478 467 485 T_(N)/° C. 500 580 500 500 500 510 510 500 490 510 t_(N)/min 120 5 10 10 10 10 10 10 10 10 T_(c)/° C. 650 700 700 600 650 t_(c)/min 10 60 20 120 60 Main Li₂Si₂O₅ Li₂Si₂O₅ Li₂SiO₃ Li₂SiO₃ crystal phase Other Li₂SiO₃ Li₂SiO₃, crystal Li₃PO₄ phases T_(FC)/° C. 950 880 920 905 920 875 900 875 900 920 t_(FC)/min 5 7 7 30 60 30 30 10 10 7 T_(press)/° C. t_(Press)/min Main Li₂Si₂O₅ Li₂Si₂O₅ Li₂Si₂O₅ Li₂Si₂O₅ Li₂Si₂O₅ Li₂Si₂O₅ Li₂Si₂O₅ Li₂Si₂O₅ Li₂Si₂O₅ Li₂Si₂O₅ crystal phase Other Li₃PO₄ Li₃PO₄ Li₃PO₄ Li₃PO₄ Li₂SiO₃ Li₂SiO₃ Li2Si02 Li₃PO₄ CAS Li₃PO₄ crystal CAS CAS CAS CAS CAS Li₃PO₄ Li₃PO₄ CAS CAS phases SiO₂ LAS CAS CAS LAS AlPO₄ L* a* b* CR CTE_(100-400° C.)/ 13.2 11.8 16.7 9.0 13.1 9.0 16.5 10⁻⁶ · K⁻¹ K_(IC)/ 2.6 2.8 MPa m^(0.5) σ_(B)/MPa 614 334 260 350 CAS = Cs_(0.809) (AlSi₅O₁₂); LAS = Li₂O*Al₂O₃*7.5 SiO₂ L*,a*,b*: colour coordinates of the samples, determined according to DIN 5033 and DIN 6174 CR: contrast value as a measure of the translucence, determined according to BS 5612 Example 21 22 23 24 25 26 27 28 Composition wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% wt.-% SiO₂ 69.1 69.0 69.0 68.7 67.6 70.6 68.8 67.5 Li₂O 14.3 13.3 12.6 12.0 12.4 13.6 13.2 11.8 Cs₂O 4.7 8.3 7.8 7.3 7.6 4.5 4.4 7.2 Al₂O₃ 1.7 3.7 3.8 4.0 3.7 5.6 5.4 3.9 P₂O₅ 3.1 2.9 2.7 2.5 2.6 2.9 2.8 2.5 Na₂O — 0.7 1.0 1.4 1.0 0.7 0.7 1.3 K₂O — 0.7 1.1 1.5 1.1 0.7 0.7 1.4 CaO — 0.1 0.2 0.5 0.2 0.1 0.1 0.3 SrO — 0.2 0.3 0.4 0.3 0.2 0.2 0.4 ZnO — 0.3 0.5 0.6 0.5 0.3 0.3 0.6 Y₂O₃ — — — — — — — — La₂O₃ — — — — — — — — TiO₂ 7.1 0.2 0.2 0.3 0.2 0.2 0.2 0.3 GeO₂ — — — — — — — — ZrO₂ — 0.1 0.1 0.1 0.1 0.1 0.1 0.1 CeO₂ — 0.1 0.1 0.1 2.0 0.1 2.0 2.0 V₂O₅ — — — — 0.1 — 0.1 0.1 Ta₂O₅ — — — — — — — — Tb₄O₇ — — — — — — 0.4 — Er₂O₃ — — — — — — 0.2 — B₂O₃ — 0.2 0.3 0.3 0.3 0.2 0.2 0.3 F — 0.2 0.3 0.3 0.3 0.2 0.2 0.3 T_(g)/° C. 495 456 453 450 456 458 450 456 T_(N)/° C. 520 480 470 470 480 480 470 480 t_(N)/min 10 10 10 10 10 10 10 10 T_(c)/° C. 750 t_(c)/min 20 Main crystal Li₂SiO₃ phase Other crystal phases T_(FC)/° C. 870 860 t_(FC)/min 7 60 T_(press)/° C. 950 920 900 920 930 900 890 t_(Press)/min 25 25 25 25 25 25 25 Main crystal Li₂Si₂O₅ Li₂Si₂O₅ Li₂Si₂O₅ Li₂Si₂O₅ Li₂Si₂O₅ Li₂Si₂O₅ Li₂Si₂O₅ Li₂Si₂O₅ phase Other crystal Li₃PO₄ Li₃PO₄ Li₃PO₄ Li₃PO₄ Li₃PO₄ Li₃PO₄ Li₃PO₄ Li₃PO₄ phases CAS CAS CAS CAS CAS small small CAS TiO₂ amount amount of CAS of CAS L* 79.3 74.8 82.6 a* 4.5 7.4 1.5 b* 30.9 32.1 33.1 CR 77 79 78 65 CTE_(100-400° C.)/ 11.9 12.1 11.3 11.4 8.8 9.8 11.6 10⁻⁶ · K⁻¹ K_(IC)/ MPa m^(0.5) σ_(B)/MPa 319 (900° C./7 min) CAS = Cs_(0.809) (AlSi₅O₁₂) L*,a*,b*: colour coordinates of the samples, determined according to DIN 5033 and DIN 6174 CR: contrast value as a measure of the translucence, determined according to BS 5612 

The invention claimed is:
 1. Process of using a lithium silicate glass ceramic or a lithium silicate glass which comprise the following components Component wt.-% SiO₂ 54.0 to 78.0 Li₂O 11.0 to 19.0 Cs₂O 4.4 to 13.0 Al₂O₃ 1.0 to 9.0 P₂O₅ 0.5 to 9.0,

for coating a substrate selected from oxide ceramics, metals and alloys.
 2. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise at least one of the following components in the given amounts Component wt.-% SiO₂ 55.1 to 77.1 Li₂O 11.8 to 17.8 Cs₂O 4.4 to 11.7 Al₂O₃ 1.7 to 8.0 P₂O₅ 1.3 to 7.5 ZrO₂ 0 to 4.5 Transition metal oxide 0 to 7.5,

wherein the transition metal oxide is selected from the group consisting of oxides of yttrium, oxides of transition metals with an atomic number from 41 to 79 and mixtures of these oxides.
 3. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise up to 70.0 wt.-% SiO₂.
 4. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise 5.0 to 10.0 wt.-% Cs₂O.
 5. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise 2.0 to 6.0 wt.-% Al₂O₃.
 6. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise less than 4.0 wt.-% Na₂O and/or K₂O.
 7. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise less than 2.5 wt.-% Rb₂O.
 8. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise less than 3.8 wt.-% BaO.
 9. Process according to claim 1, in which a lithium silicate glass ceramic is used which comprises lithium metasilicate as main crystal phase.
 10. Process according to claim 1, in which a lithium silicate glass ceramic is used which comprises lithium disilicate as main crystal phase.
 11. Process of using a lithium silicate glass ceramic which comprises the following components Component wt.-% SiO₂ 54.0 to 78.0 Li₂O 11.0 to 19.0 Cs₂O  4.0 to 13.0 Al₂O₃ 1.0 to 9.0 P₂O₅  0.5 to 9.0,

for coating a substrate selected from oxide ceramics, metals and alloys, in which the lithium silicate glass ceramic comprises at least one caesium aluminosilicate crystal phase.
 12. Process of using a lithium silicate glass ceramic which comprises the following components Component wt.-% SiO₂ 54.0 to 78.0 Li₂O 11.0 to 19.0 Cs₂O  4.0 to 13.0 Al₂O₃ 1.0 to 9.0 P₂O₅  0.5 to 9.0,

for coating a substrate selected from oxide ceramics, metals and alloys, in which the lithium silicate glass ceramic comprises at least one lithium aluminosilicate crystal phase.
 13. Process according to claim 1, in which a lithium silicate glass is used, wherein the lithium silicate glass comprises nuclei which are suitable for forming lithium metasilicate and/or lithium disilicate crystals.
 14. Process according to claim 1, in which the substrate is an oxide ceramic.
 15. Process of using a lithium silicate glass ceramic which comprises the following components Component wt.-% SiO₂ 54.0 to 78.0 Li₂O 11.0 to 19.0 Cs₂O  4.0 to 13.0 Al₂O₃ 1.0 to 9.0 P₂O₅  0.5 to 9.0,

for coating a substrate in which the substrate is a metal or an alloy.
 16. Process according to claim 1, in which the substrate is a dental restoration.
 17. Process for coating a substrate selected from oxide ceramics, metals and alloys, in which a lithium silicate glass ceramic or a lithium silicate glass, as defined in claim 1, is applied to the substrate.
 18. Process according to claim 17, in which the lithium silicate glass ceramic or the lithium silicate glass is applied to the substrate by sintering or by pressing-on.
 19. Process according to claim 17, in which the lithium silicate glass ceramic or the lithium silicate glass is applied to the substrate by joining.
 20. Process according to claim 19, in which the lithium silicate glass ceramic or the lithium silicate glass is shaped to a desired geometry by machining or by hot pressing before joining.
 21. Process according to claim 17, in which a coating is obtained which comprises a lithium silicate glass ceramic that comprises lithium metasilicate as main crystal phase.
 22. Process according to claim 17, in which a coating is obtained which comprises a lithium silicate glass ceramic that comprises lithium disilicate as main crystal phase.
 23. Process according to claim 21, in which the lithium silicate glass ceramic comprises at least one caesium aluminosilicate crystal phase.
 24. Composite material which comprises a lithium silicate glass ceramic or a lithium silicate glass, as defined in claim 1, on a substrate selected from oxide ceramics, metals and alloys.
 25. Lithium silicate glass ceramic, which is as defined in claim 11 and which comprises at least one caesium aluminosilicate crystal phase.
 26. Lithium silicate glass ceramic, which is as defined in claim 1 and which comprises the following components in the given amounts Component wt.-% SiO₂ 54.0 to 78.0, Li₂O 11.0 to 19.0 Cs₂O 4.6 to 13.0 Al₂O₃ 1.0 to 9.0 P₂O₅ 0.5 to 9.0 Rb₂O 0 to 7.0 BaO 0 to 3.7 ZrO₂ 0 to 4.5 Transition metal oxide 0 to 7.5,

wherein the transition metal oxide is selected from the group consisting of oxides of yttrium, oxides of transition metals with an atomic number from 41 to 79 and mixtures of these oxides.
 27. Lithium silicate glass, which comprises the components of the glass ceramic according to claim
 26. 28. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise at least one of the following components in the given amounts Component wt.-% SiO₂ 55.1 to 77.1 Li₂O 11.8 to 17.8 Cs₂O 4.4 to 11.7 Al₂O₃ 1.7 to 8.0 P₂O₅ 1.3 to 7.5 ZrO₂ 0 to 4.0 Transition metal oxide 0 to 7.0,

wherein the transition metal oxide is selected from the group consisting of oxides of yttrium, oxides of transition metals with an atomic number from 41 to 79 and mixtures of these oxides.
 29. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise 60.0 to 70.0 wt.-% SiO₂.
 30. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise 64.0 to 70.0 wt.-% SiO₂.
 31. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise 5.1 to 8.0 wt.-% Cs₂O.
 32. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise 5.5 to 7.7 wt.-% Cs₂O.
 33. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise 6.1 to 7.4 wt.-% Cs₂O.
 34. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise 2.5 to 5.0 wt.-% Al₂O₃.
 35. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise 3.0 to 4.5 wt.-% Al₂O₃.
 36. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise less than 3.5 wt.-% Na₂O and/or K₂O.
 37. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise less than 3.0 wt.-% Na₂O and/or K₂O.
 38. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise less than 2.5 wt.-% Na₂O and/or K₂O.
 39. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise less than 2.0 wt.-% Na₂O and/or K₂O.
 40. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise less than 1.5 wt.-% Rb₂O.
 41. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise less than 1.0 wt.-% Rb₂O.
 42. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise less than 0.5 wt.-% Rb₂O.
 43. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass is substantially free of Rb₂O.
 44. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise less than 2.5 wt.-% BaO.
 45. Method according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise less than 1.5 wt.-% BaO.
 46. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass comprise less than 0.5 wt.-% BaO.
 47. Process according to claim 1, in which the lithium silicate glass ceramic or the lithium silicate glass is substantially free of BaO.
 48. Process according to claim 1, in which a lithium silicate glass ceramic is used which comprises lithium metasilicate as main crystal phase and has a bending strength in the range of about 180 to 300 MPa and/or a fracture toughness, measured as K_(IC) value, of at least about 2.3 MPa·m^(0.5).
 49. Process according to claim 1, in which a lithium silicate glass ceramic is used which comprises lithium metasilicate as main crystal phase and has a bending strength in the range of about 180 to 300 MPa and/or a fracture toughness, measured as K_(IC) value, of at least about 2.6 MPa·m^(0.5).
 50. Process according to claim 1, in which a lithium silicate glass ceramic is used which comprises lithium disilicate as main crystal phase and has a bending strength in the range of about 400 to 700 MPa and/or a fracture toughness, measured as K_(IC) value, of at least about 2.3 MPa·m^(0.5).
 51. Process according to claim 1, in which a lithium silicate glass ceramic is used which comprises lithium disilicate as main crystal phase and has a bending strength in the range of about 400 to 700 MPa and/or a fracture toughness, measured as K_(IC) value, of at least about 2.6 MPa·m^(0.5).
 52. Process according to claim 11, in which a lithium silicate glass ceramic is used which comprises at least one caesium aluminosilicate crystal phase, wherein the caesium aluminosilicate has the formula Cs_(x)AlSi₅O₁₂, wherein x is 0.75 to 0.85.
 53. Process according to claim 11, in which a lithium silicate glass ceramic is used which comprises at least one caesium aluminosilicate crystal phase, wherein the caesium aluminosilicate has the formula Cs_(x)AlSi₅O₁₂, wherein x is 0.80 to 0.82.
 54. Process according to claim 11, in which a lithium silicate glass ceramic is used which comprises at least one caesium aluminosilicate crystal phase, wherein the caesium aluminosilicate has the formula Cs_(x)AlSi₅O₁₂, wherein x is 0.808 to 0.810.
 55. Process according to claim 11, in which a lithium silicate glass ceramic is used which comprises at least one caesium aluminosilicate crystal phase, wherein the caesium aluminosilicate has the formula Cs_(0.809)AlSi₅O₁₂.
 56. Process according to claim 1, in which the substrate is a zirconium oxide ceramic.
 57. Process according to claim 15, in which the substrate is non-precious metal alloy.
 58. Lithium silicate glass ceramic, which is as defined in claim 1 and which comprises the following components in the given amounts Component wt.-% SiO₂ 55.1 to 77.1 Li₂O 11.8 to 17.8 Cs₂O 4.7 to 11.7 Al₂O₃ 1.7 to 8.0 P₂O₅ 1.3 to 7.5 Rb₂O 0 to 5.0 BaO 0 to 3.0 ZrO₂ 0 to 4.0 Transition metal oxide 0 to 7.0,

wherein the transition metal oxide is selected from the group consisting of oxides of yttrium, oxides of transition metals with an atomic number from 41 to 79 and mixtures of these oxides.
 59. Process according to claim 1, in which a lithium silicate glass ceramic is used which comprises lithium metasilicate as main crystal phase and has a bending strength in the range of about 180 to 300 MPa and/or a fracture toughness, measured as K_(IC) value, of at least about 2.0 MPa·m^(0.5).
 60. Process according to claim 1, in which a lithium silicate glass ceramic is used which comprises lithium disilicate as main crystal phase and has a bending strength in the range of about 400 to 700 MPa and/or a fracture toughness, measured as K_(IC) value, of at least about 2.0 MPa·m^(0.5).
 61. Process according to claim 11, in which a lithium silicate glass ceramic is used which comprises at least one caesium aluminosilicate crystal phase, wherein the caesium aluminosilicate has the formula Cs_(X)AlSi₅O₁₂, wherein x is 0.70 to 0.90.
 62. Process according to claim 12, in which a lithium silicate glass ceramic is used which comprises at least one lithium aluminosilicate crystal phase, wherein the lithium aluminosilicate has the formula Li₂O*Al₂O₃*7.5SiO₂.
 63. Process according to claim 16, in which the dental restoration is a bridge, an inlay, an onlay, a veneer, an abutment, a partial crown, a crown or a facet.
 64. Process according to claim 17, in which a coating is obtained which comprises a lithium silicate glass ceramic that comprises lithium metasilicate as main crystal phase, and which has a bending strength in the range of about 180 to 300 MPa and/or a fracture toughness, measured as K_(IC) value, of at least about 2.0MPa·m^(0.5).
 65. Process according to claim 17, in which a coating is obtained which comprises a lithium silicate glass ceramic that comprises lithium disilicate as main crystal phase, and which has a bending strength in the range of about 400 to 700 MPa and/or a fracture toughness, measured as K_(IC) value, of at least about 2.0MPa·m^(0.5).
 66. Process according to claim 21, in which the lithium silicate glass ceramic comprises at least one caesium aluminosilicate crystal phase, wherein the caesium aluminosilicate has the formula Cs_(X)AlSi₅O₁₂, wherein x is 0.70 to 0.90.
 67. Process according to claim 21, in which the lithium silicate glass ceramic further comprises at least one lithium aluminosilicate crystal phase.
 68. Process according to claim 21, in which the lithium silicate glass ceramic further comprises at least one lithium aluminosilicate crystal phase, wherein the lithium aluminosilicate has the formula Li₂O*Al₂O₃*7.5SiO₂. 